JP4211012B2 - Multilayer material, its manufacturing method and application - Google Patents

Description

【００７７】
すべての場合に、フィルム形成後Ｔトランス（Ttrans）よりも低い温度に冷却して、殺ウイルス剤を適正に保持した弾性且つ柔軟性のゲルが得られる。
【００７８】
これらの組成物は、２５℃で測定することにより得られた、図５及び６の三成分ダイヤグラムに合致している。
【００７９】
実施例３： 可逆的に架橋された層Ａの調製
調製は、バーダック（登録商標）を、アルドリッチ（Aldrich）社から照会番号86,056-5で市販されているポリビニルピロリドン−ヨウ素コンプレックスに置き換える以外は、実施例１及び２と同様にして行う。
【００８０】
ポリビニルピロリドン−ヨウ素コンプレックスを、６０℃で撹拌下、水とゼラチンの混合液中に、５重量％のポリビニルピロリドン−ヨウ素コンプレックス溶液が得られるように、溶解する。
【００８１】
形成されたクリアな溶液は、１５重量％のゼラチンを含有している。
【００８２】
混合液の温度（６０℃）は、ゲル−液体転移温度よりも高い温度に相当する。この転移温度はその温度で混合液の粘度が突然変化することで決定され、この場合は３０−３５℃である。
【００８３】
フィルムＡは、１００μｍの制御厚を有するフィルムドローワーを用いて５０℃で、フィルム状とする予め決められた条件で、この溶液を冷却している間に調製される。
【００８４】
かくして得られたフィルムＡは、良好な弾性と柔軟性を有し、殺ウイルス剤を適正に保持している。
【００８５】
実施例４： 可逆的に架橋された層Ａの調製
この実施例において、構造ポリマーｃは、サイテック(Cytec)社からＮ ３００という名称で販売されているポリアクリルアミド（ＰＡＡｍ）である。ＰＡＡｍを、水中で０．１〜０．５％の溶液になるように攪拌しながら溶解する。フィルムＡは、セラミックフォーマー上で水を蒸発させた後に得られる。得られたフィルムは良い弾性を有している。
【００８６】
実施例５： 可逆的に架橋された層Ａを有する三層の多層材料の調製
この実施例は、二つのバリアー層Ｅの間に挿入された層Ａからなるシンプルな多層材料の調製に関する。
【００８７】
ポリイソプレン（ＰＩ）を、１５重量％のＰＩ含有溶液となるようにシクロヘキサン中で攪拌しながら溶解する。
【００８８】
２００μｍの制御厚を有するフィルムドローワーを使用して、エラストマーのシクロヘキサン溶液でガラス物質をコーティングすることにより、厚さ６０μｍの層Ｅを調製する。これを行うためには二工程が必要である。ポリイソプレンを１５％含むシクロヘキサン溶液を用いる。
【００８９】
この層に、実施例１又は２に記載される同一の工程に従って調製されるバーダック（登録商標）、ゼラチン及びエチレングリコールを０．５／２／１０の割合で含む５０μｍの層Ａが加えられる。
【００９０】
次いで、該層Ａ上に、第２の６０μｍ厚のエラストマー・バリアー層Ｅが調製される。
【００９１】
実施例６： 可逆的に架橋された層Ａの調製
この実施例において、構造ポリマーｃは、加水分解率が８８％且つ粘度が２０℃下４％水溶液について２６ｍＰａ.ｓであることで特徴づけられるモウィオール（Mowiol：登録商標）26-88タイプのポリビニルアルコール（ＰＶＡ）である。
【００９２】
モウィオール（登録商標）は、８０℃で攪拌下、７．５％モウィオール（登録商標）溶液が得られるように水／ＰＥＧ混合液に溶解される。バーダック（登録商標）を、この溶液に７６．５％含まれるように添加する。
【００９３】
フィルムＡは、該溶液中にセラミックフォーマーを浸漬(dipping)し、７０℃で水を蒸発することによって得られる。得られたフィルムは良い弾性を有している。
【００９４】
実施例７： 可逆的に架橋された層Ａを含む５層の多層材料の調製
この実施例は、二つのバリアー層Ｅの間に挿入された層Ａからなり、接着が結合層Ｚによって改善されている、多層材料の調製に関する。
【００９５】
実施例５と同様にして、フォーマーをＰＩを１５％含むシクロヘキサン溶液中に浸漬することによって、層Ｅを調製する。無水マレイン酸で処理したＳＥＢＳで構成されており、１５％ＳＥＢＳを含むようシクロヘキサンで希釈されて、クラトン（Kraton）1901（シェル（Shell）社）の名称で販売されている結合層を、この層に加える。溶媒を蒸発させた後、実施例６と同一の層Ａを浸漬することによって得る。結合層、次いで最後のエラストマー層を上記の記載に従って調製する。
【００９６】
実施例８： 可逆的に架橋された層Ａを含む５層の多層材料の調製
調製は、無水マレイン酸で処理したＳＥＢＳを、アクリル酸／エチレンコポリマーを３％含むトルエン溶液に置き換える以外は、実施例７と同様に行う。該コポリマーは、デュポン（Dupont）社からヴァマック（Vamac、登録商標）の名称で販売されているか、又はエキソン（Exxon）社からＡＴＸ（登録商標）の名称で販売されている。
【００９７】
実施例９： 可逆的に架橋された層Ａを含む５層の多層材料の調製
調製は、無水マレイン酸で処理したＳＥＢＳを、フルス（Huls）社からシロライト（Cyrolite、登録商標）G20の名称で販売されているメタクリレート／スチレンコポリマーを３％含むトルエン溶液に置き換える以外は、実施例７と同様に行う。
【００９８】
実施例１０： 可逆的に架橋された層Ａを含む三層の多層材料の調製
この実施例は、二つのバリアー層Ｅの間に挿入された層Ａからなり、接着が層Ａ中にある結合剤ｙによって改善されている多層材料の調製に関する。
【００９９】
第１のエラストマー層を、上記実施例と同様にして得る。エルフ アトケム（Elf Atochem）社からSMA 1440Hの名称で販売されている３％ブタジエン−スチレン−無水マレイン酸コポリマーを、層Ａの製造に使用する溶液に加える。第２のバリアー層Ｅを上述のごとく得る。
【０１００】
実施例１１： 可逆的に架橋された層Ａ及び結合層Ｚを有する５層の多層材料
この実施例は、２つのバリアー層Ｅの間に挿入されたＡ層からなり、それらの層間の接着が結合層Ｚにより改善されている多層材料の調製に関する。
【０１０１】
実施例５と同様にして、厚さ６０μｍの層Ｅを、２００μｍの制御厚を有するフィルムドローワーを用いて、ガラス物質をエラストマーのシクロヘキサン溶液でコーティングすることにより調製する。これを行うためには、二工程が必要である。ポリイソプレンを１５％含むシクロヘキサン溶液を使用する。
【０１０２】
この層に、５０μｍ厚を有するフィルムドローワーを用いて、ローム アンドハース（Rohm & Haas)社から、固形内容物を５５％有する分散水溶液の形態で包装されてプライマル（Primal：登録商標）EP 6010 K という名称で販売されている、アクリル樹脂ラテックスから構成される結合層を加える。
【０１０３】
結合層を形成するために５０℃で水を蒸発後、層Ａを、５０μｍの厚さを有するフィルムドローワーを用いて５０℃で適用し、次いで柔軟性と弾性のあるフィルムが形成されるまで冷却する。
【０１０４】
最後に、厚さ５０μの結合層Ｚ、次いで厚さ６０μの最後のエラストーマー層Ｅを上述に従って調製する。
【０１０５】
得られた多層材料は、５層を含んでおり、許容できる弾性、許容できる柔軟性及び許容できる内部層間の接着を示す。
【０１０６】
実施例１２： 可逆的に架橋された層Ａ、及び層Ｅに混合された結合剤ｙを有する三層の多層材料の調製
この実施例は、２つのバリアー層Ｅの間に挿入された層Ａからなり、これら層間の接着が層Ｅに入れられた結合剤ｙにより改善されている多層材料の調製に関する。
【０１０７】
ポリイソプレン（ＰＩ）を、１５重量％のＰＩ含有溶液となるように、攪拌しながらシクロヘキサンに溶解する。
【０１０８】
この溶液に、５１５００ダルトンの分子量を有し、１モルのポリオキシエチレン構成物を２０％含有するポリブタジエン−ブロック−ポリオキシエチレン ジ−ブロックコポリマーを添加し、５％のコポリマーを含有する溶液を得る（完全溶液に関して質量で表現される）。
【０１０９】
厚さ６０μｍのフィルムＥは、５０℃で溶媒を蒸発することにより実施例５に記載するようにして得られる。
【０１１０】
５０μｍの厚さの層Ａ、次いで６０μｍの厚さの層Ｅを上の実施例１１の記載に従って調製する。
【０１１１】
多層材料は三層を含み、許容される弾性、許容される柔軟性及び許容される層間の接着を示す。
【０１１２】
実施例１３： 可逆的に架橋された層Ａを有し、層Ａに混合された結合剤ｙを有する三層の多層材料の調製方法
調製は、結合剤を層Ａに入れる以外は、実施例１２と同じようにして行われる。
【０１１３】
酸処理によりコラーゲンから生じ且つ１７５のブルーム値（Bloom value）を有するゼラチンを、ゲルに関してバーダック（登録商標）を１０重量％含有する、バーダック（登録商標）とエチレングリコールとの混合液中で、６０℃攪拌下で、溶解する。
【０１１４】
形成されたクリアな溶液は１５重量％のゼラチンを含んでいる。
【０１１５】
この溶液に、ゴールドシュミット エージー(Goldschmidt AG) 社によりブリノイル (Brinoil) (登録商標）LE 2362 という名称で販売されている、アルキル主鎖上にポリオキシエチレンとアクリル鎖の構成を含むグラフトコポリマーを加える。
【０１１６】
最終溶液は、ゲルに関して５％のグラフトコポリマーを含んでいる。
【０１１７】
５０μｍの制御厚を有するフィルムドローワーを用いて５０℃で、フィルム状になるよう予め条件付けられた下で、この溶液を冷却することによって、層Ａを得る。
【０１１８】
層Ａの両面上に６０μｍの厚さの層Ｅを、実施例１１に示された内容と類似の方法で調製する。
【０１１９】
実施例１４： 二つの異なる殺ウイルス剤を有し且つ可逆的に架橋された二つの層Ａ、及び結合層Ｚを有する６層の多層材料の調製
厚さ６０μｍのエラストマー層Ｅ、次いで厚さ５０μｍの結合層Ｚを、実施例１１と同様にして調製する。
【０１２０】
次いで、第１の厚さ５０μｍの層Ａを加える。該層Ａは、実施例１に記載の活性化学物質ｘとしてバーダック（登録商標）を含む混合物を用いたものである。
【０１２１】
第２の、厚さがまた５０μｍの層Ａを調製する。該層Ａは、実施例３に従って活性化学物質ｘとしてポリビニルピロリドン−ヨウ素コンプレックスを含む混合物を用いたものである。
【０１２２】
次いで、実施例１１に記載するように、この第２の層Ａに、５０μｍの結合層Ｚ、次いで最後のエラストマー層Ｅが付加される。
【０１２３】
かくして得られる多層材料は、許容される弾性、許容される柔軟性及び許容される層間の接着を示す。
【０１２４】
実施例１５： 可逆的に架橋された層Ａを有し且つ層Ａに混合される結合剤ｙを含有する、”完全に水性の”プロセスで調製される三層の多層材料の調製
調製は、ポリイソプレンのシクロヘキサン溶液を、６０.５％の固形内容物を含む、レブルテックス（Revultex：登録商標）LA の名称で販売されている予備加硫化(prevulcanized)天然ゴムラテックスに置き換える以外は、実施例１３と同様にして行われる。
【０１２５】
その粘度は２０℃で７０ｍＰａ.ｓである。
【０１２６】
９０μｍの厚さの層Ｅは、１５０μｍの制御厚を有するフィルムドローワーを用いて、ガラス物質を予備加硫化ラテックスでコーティングすることにより調製される。
【０１２７】
層Ｅのエラストマーラテックスから水を蒸発させ、６０℃で加硫した後、層Ａを実施例１３の記載に従って適用し、次いで最後の層Ｅを調製する。
【０１２８】
かくして得られた多層材料は、許容される弾性、許容される柔軟性及び許容される内部層間の接着を示す。
【０１２９】
実施例１６： 可逆的に架橋された層Ａを有し、結合剤Ｚを有しかつ完全に水系プロセスにより調製される５層状の多層材料の調製
調製は、予備加硫化天然ゴムラテックス、レブルテックス（登録商標）LAを使用して実施例１１のように行われる。
【０１３０】
厚さ９０μｍの層Ｅは、１５０μｍの制御厚を有するフィルムドローワーを用いて、ガラス物質を予備加硫化ラテックスでコーティングすることにより調製される。
【０１３１】
層Ｅのエラストマーラテックスから水を蒸発させ、６０℃で加硫した後、アクリルラテックス（プライマル EP60-10 タイプ）からなる厚さ５０μｍの結合層Ｚを実施例７の記載に従って適用する。
【０１３２】
次いで、厚さ５０μｍの層Ａを加える。該層Ａは、実施例１に記載の、活性化学物質ｘとしてバーダック（登録商標）を含む混合物を用いるものである。
【０１３３】
最後に、厚さ５０μｍの結合層Ｚ、次いで厚さ９０μｍの最後のエラストマー層Ｅを上述に従って調製する。
【０１３４】
かくして得られた多層材料は、許容される弾性、許容される柔軟性及び許容される層間の接着を示す。
【０１３５】
実施例１７： γ線照射により架橋された層Ａを含む三層の多層材料の調製
８％のＰＶＰ水溶液を調製し、二つのガラスプレートの１ｍｍ間隔の間に注ぐ。このシステムを、０.６６rad／分の強さを有する⁶⁰Ｃｏ源から３１.５ｃｍ離れたところに１ヶ月間置く。かくして得られたゲルは、良好な柔軟性を有している。
【０１３６】
実施例１８： 非可逆的に架橋された層Ａを含む三層の多層材料の調製
この実施例は、二つのバリアー層Ｅの間に挿入された層Ａからなり、該層Ａが架橋されている、多層材料の調製に関する。
【０１３７】
第１のエラストマー層を、実施例５と同様にして得る。３％グルタルアルデヒドを、実施例１記載の層Ａに加える。第２のバリアー層Ｅを上述のごとく得る。
【０１３８】
実施例１９： 非可逆的に架橋された層Ａを含む三層の多層材料の調製
この実施例は、二つのバリアー層Ｅの間に挿入された層Ａからなり、該層Ａが架橋されている、多層材料の調製に関する。
【０１３９】
第１のエラストマー層を、上記実施例と同様にして得る。層Ａを実施例１と同じようにしてバーダック（登録商標）、ゼラチン及びエチレングリコールを含有する溶液に浸漬することによって取得し、次いでフォーマー(former:浸漬型）をグルタルアルデヒドを３％含むアセトン溶液中に浸漬(immerse)する。蒸発させた後、フォーマーを、再度エラストマー溶液に浸漬する。
【０１４０】
実施例２０： 非可逆的に架橋された層Ａの調製
この実施例においては、構造ポリマーｃは、分子量が８８０００ダルトン且つ加水分解率が９９％であることで特徴付けられるモウィオール(登録商標）28-99タイプのポリビニルアルコールである。その粘度は、２０℃の４％水溶液で、２８mPa.sである。
【０１４１】
モウィオール（登録商標）を、撹拌下８０℃で、２.５％モウィオール（登録商標）溶液が得られるように、水（溶媒ｓ _a）に溶解する。
【０１４２】
この溶液に、トライトン Ｘ１００（登録商標）（活性化学物質ｘ）を、１０％トライトン（モウィオール(登録商標）溶液に関して表現する）を含むクリアな溶液が得られるまで攪拌しながら添加する。
【０１４３】
得られたクリアな溶液は粘性のある液体の形態で提供される。
【０１４４】
非可逆的な架橋剤ｉｃを含む溶液を、モルベースで塩酸１部あたり水を９部含有する水／塩酸混合液中に、溶液に０.００５％のグルタルアルデヒドを含むように、グルタルアルデヒドを混合して調製する。
【０１４５】
層Ａは、１０重量部のモウィオール（登録商標）含有溶液を、０．０４７５重量部の非可逆的架橋剤含有溶液と同時に噴霧することによって調製される。
【０１４６】
このように調製された層Ａは、許容される弾性及び許容される柔軟性を示す。
【０１４７】
実施例２１： 非可逆的に架橋された層Ａを含み、その内部層間の接着がエラストマー層Ｅの処理によって得られる三層の多層材料の調製
この実施例は、二つのバリアー層Ｅの間に挿入された層Ａからなり、その接着がエラストマー層の化学的処理によって得られる、多層材料の調製に関する。
【０１４８】
エラストマー層は、セラミックフォーマーを、スチレン−イソプレン−スチレン（ＳＩＳ）（又はスチレン−ブタジエン−スチレン（ＳＢＳ））コポリマーを１５％含むシクロヘキサン溶液に浸漬することによって調製される。溶媒を蒸発させた後、フォーマーを、オニアクロル（Oniachlor、登録商標）（ボスティック（Bostik）社から販売されている）の２５ｇ／ｌ水溶液中に５分間、浸漬する。
【０１４９】
超純水（ultrapure water）ですすぐことにより、過剰の産物を除去することが可能である。次いで、層Ａを実施例６と同様にして得る。最後のエラストマー層を実施例５と同様にして加える。
【０１５０】
層の接着は許容できる。
【０１５１】
実施例２２： 非可逆的に架橋された層Ａが互いに浸透し合った網状構造(interpenetrated network)である三層の多層材料の調製
第１のエラストマー層Ｅを上記実施例と同様にして得る。調製は、ゼラチンを溶解する点に関しては、実施例１と同様にして行う。その後、ＡＡｍ、Ｎ，Ｎ’−ビスアクリルアミド、ＡＡｍ用架橋剤ｉｃ、レドックス開始剤Ｉ及びゼラチン用架橋剤ｉｃ’、グルタルアルデヒドを、該溶液に加える。その後、フォーマーをバーダック（登録商標）を含むこの溶液中に浸漬する。水を蒸発させた後に、上述したようにＳＥＢＳ層で覆う。
【０１５２】
実施例２３： 層Ａが現場重合によって得られるものである、三層の多層材料の調製
エラストマー層Ｅを、実施例５と同様にして調製する。層Ａを、ヒドロキシエチルメタクリレート（ＨＥＭＡ）、質量が４００のポリエチレングリコール及びバーダック（登録商標）を１／１／１の割合で含む混合液に、フォーマーを浸漬することによって調製する。更に重合は、Ｎａ₃Ｓ₃Ｏ₅及び（ＮＨ₄）₂Ｓ₂０₈の存在下、７０℃で開始される。最終のエラストマー層を実施例５と同様に加える。
【０１５３】
実施例２４： 層Ａが架橋剤ｉｃの存在下での現場重合によって得られるものである三層の多層材料の調製
エラストマー層Ｅを、実施例５と同様して調製する。０．３％エチレングリコールジメタクリレート（ポリマーの質量によって表される）を、架橋剤ｉｃとして実施例２３記載の混合液に加える。
【０１５４】
重合を、ＡＩＢＮの存在下、７０℃で開始する。
【０１５５】
第２のエラストマーバリアー層Ｅを、実施例５に記載の浸漬方法（ディッピング方法）によって層Ａ上に調製する。
【０１５６】
実施例２５： 層Ａが架橋剤ｉｃの存在下での現場重合によって得られるものである、三層の多層材料の調製
エラストマー層Ｅを、実施例５と同様に調製する。層Ａを加える。該層Ａは、アクリルアミド、エチレングリコール、水、架橋剤ｉｃとしてＮ，Ｎ’−ビスアクリルアミド（ＮＢＡＡｍ）及びバーダック（登録商標）を含む混合物を用いて、
実施例６に従うものである。重合を、レドックス開始剤の存在下、室温で開始する。
【０１５７】
第２のエラストマーバリアー層Ｅを、実施例５に記載の浸漬方法によって層Ａ上に調製する。
【０１５８】
実施例２６： 層Ａが増粘剤ｆの存在下での現場重合によって得られるものである、三層の多層材料の調製
エラストマー層Ｅは、ポリクロロプレンラテックス溶液中への浸漬によって得られる。
【０１５９】
０．５％シリカを、増粘剤ｆとして実施例２３の混合液に加える。重合を、ベンゾイルペルオキシドの存在下、７０℃で開始する。
【０１６０】
第２のエラストマーバリアー層Ｅを、１５％ポリウレタン溶液中にフォーマーを浸漬することによって、層Ａ上に調製する。
【０１６１】
実施例２７： 層Ａがゲルと同じ化学的性質の増粘剤ｆの存在下における現場重合により得られるものである、三層の多層材料の調製。
【０１６２】
バリアー層Ｅを、実施例５と同じ方法により得る。実施例２３と同じ条件に従ってＨＥＭＡ、バーダック（登録商標）及びＰＥＧを３／１／１の割合で含み、またＢＰの存在下で予め大量に合成されたＰＨＥＭＡを含有する層Ａを、同じ方法により層Ｅに加える。
【０１６３】
最後のエラストマー層を、実施例５のように加える。
【０１６４】
実施例２８： 層Ａが増粘剤ｆの存在下及び接着層Ｚの存在下における現場重合により得られたものである、５層の多層材料の調製。
【０１６５】
バリアー層Ｅを、実施例５と同じ方法により得る。フォーマーをヴァマック（Vamac）溶液に浸漬し、次いで実施例２３の条件に従って２／１／１の割合からなるＨＥＭＡ，バーダック(登録商標），ＰＥＧ、それとＢＰ（過酸化ベンゾイル）及びモダレッツ２００（Modarez 200）の名前でプロテックス（Protex）社により販売されているポリ（アクリル酸）とを含有する溶液に浸漬する。
【０１６６】
重合後、上記のようにフォーマーをエラストマー溶液Ｅに浸漬する。
【０１６７】
実施例２９： 層Ａが現場重合により得られたものであり、接着層Ｚを含有する、５層の多層材料の調製。
【０１６８】
バリアー層Ｅを、実施例５と同じ方法により得る。プライマルＥＰ６０１０Ｋ（Primal EP 6010K）の名前で販売されているアクリル樹脂ラテックスからなる結合層を、同じ方法により当該層Ｅに加える。乾燥後、層Ａを、浸漬（ディッピング）方法により付着させる。それは、水、バーダック（登録商標）及びＰＥＧ４００の存在下で、メタクリル酸メチル０〜５０％をヒドロキシエチルメタクリレート１００〜５０％と混合することにより得られるものである。
【０１６９】
開始は、７０℃下で、ＢＰを用いて行われる。ゲルを取得後、実施例５記載の第２のバリアー層Ｅで被覆する前に、フォーマーを再びプライマル溶液に浸漬する。
【０１７０】
実施例３０： 層Ａが紫外線照射により開始される現場重合により得られるものである、三層の多層材料の調製。
【０１７１】
バリアー層Ｅを、実施例５と同じ方法により得る。ＨＥＭＡ／ＮＶＰ（Ｎ−ビニルピロリドン）（７０／３０）混合物を、同じ方法により、開始剤ｉ、２−ヒドロキシ−２，２−ジメチルアセトフェノン（ダロクア１１７３（Darocur（登録商標） 1173）及び溶媒ｓ _a 、グリセロールの存在下で、層Ｅに加える。
【０１７２】
重合は、２時間紫外線照射（λ＝３６５ｎｍ）することにより開始される。ゲルを取得後、上記したように、フォーマーをエラストマー溶液Ｅ中に浸漬する。
【０１７３】
実施例３１： 層Ａが非可逆的に架橋されており、中間層間の接着がエラストマー層Ｅの処理により付与されたものである４層の多層材料の調製。
【０１７４】
本実施例は、２つのバリアー層Ｅの間に挿入された層Ａから構成される多層材料の調製に関し、その接着性は、一面はエラストマー層Ｅのプラズマ処理によるものであり、他面は接着剤層Ｚにより与えらたものである。
【０１７５】
エラストマー層Ｅは、実施例５に従って、セラミックフォーマーを１５％ＳＢＳ又はＳＩＳ溶液中に浸漬することにより得られる。
【０１７６】
該フォーマーを、該表面を酸化させるために、イオン化された窒素、アルゴン又は酸素ガスが通過するチャンバー内に置く。エラストマーの湿潤性の改善により、実施例５と同様にして得られた層との接着性が良好になる。フォーマーを、その後ゼラチン、バーダック（登録商標）及びエチレングリコールからなる溶液（実施例５に記載するように）、次いで０．３％グルタルアルデヒドを含有するアセトン溶液に浸漬し、上記したように、エラストマー層Ｅを用いて被覆する。
【図面の簡単な説明】
【図１】本発明多層材料の態様の一つ、層Ａが二つの層Ｅの間に挟まれている三層ポリメリックフィルムを示す図である。
【図２】本発明多層材料の態様の一つ、層Ｅ、層Ｚ、層Ａ、層Ｚ及び層Ｅを連続的に含む５層ポリメリックフィルムを示す図である。
【図３】本発明多層材料の態様、層Ｅ、層Ａ１、層Ａ２、層Ａ３及び層Ｅを連続的に含む５層ポリメリックフィルム、又は層Ｅ、層Ｚ、層Ａ１、層Ｚ、層Ａ２、層Ｚ、層Ａ３、層Ｚ及び層Ｅを連続的に含む９層ポリメリックフィルムを示す図である。
【図４】本発明多層材料の態様、層Ｅ、層Ａ１、層Ｅ、層Ａ２、層Ｅ、層Ａ３及び層Ｅを連続的に含む７層ポリメリックフィルム、又は層Ｅ、層Ｚ、層Ａ１、層Ｚ、層Ｅ、層Ｚ、層Ａ２、層Ｚ、層Ｅ、層Ｚ、層Ａ３、層Ｚ及び層Ｅを連続的に含む１３層ポリメリックフィルムを示す図である。
【図５】ポリマーｃ、活性物質ｘ及び溶媒ｓ _a混合物の組み合わせを示す三成分ダイヤグラムを示す。この図において斜線陰影部分はクレームされた組成の範囲に相当する。
【図６】エチレングリコール、バーダック（Bardac：登録商標）（ジメチルジデシルアンモニウム）及びゼラチンの組み合わせを例として三成分ダイヤグラムに示した図である。この図において斜線で更に囲んだ部分がクレームの範囲に相当する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a multilayer elastomeric film comprising at least one continuous layer comprising an active chemical (such as a corrosion inhibitor, a lubricant or a biocide with medical use) inserted between inert elastomer barrier layers. The present invention also relates to methods for producing these films and various applications.
[0002]
[Prior art]
Various elastomeric materials commonly used in the medical or medical-related fields are those materials (gloves, finger sacks, condoms, etc.) as described in the applicant's European Patent 306,389 or International Publication WO 95/17453. Can be modified to be combined with active chemicals that have a protective effect during use, and these publications describe an elastomeric film encapsulating a dispersion of at least one active chemical, the dispersion of which The liquid is in liquid form (International Publication WO 95/17453) or contained in microcapsules whose walls rupture under the influence of frictional or shear forces (European Patent 306,389).
[0003]
However, the production of elastomeric films by the methods described in the above applications and patents has a number of disadvantages associated with the product itself, i.e. the film or the method of obtaining the film.
[0004]
* Product related disadvantages:
-The main disadvantage of the film by either of the above two methods is that due to the fact that the chemical is dispersed in the polymer material in the form of droplets or microcapsules, the dispersion of the active chemical in the polymer material Is uneven.
[0005]
This non-uniformity of the active chemical distribution is reflected in the gaps in the active chemical, which constitutes a risk with respect to the desired protection, even if its risk is statistically very low;
The microcapsules contained in the elastomeric film according to EP 306,389 have the disadvantage that the film ruptures and releases its active substance when drilled;
-Elastomeric films containing liquid inclusions according to WO 95/17453 contain graft stabilizers or sequential copolymer (block copolymer) type polymer stabilizers which are relatively expensive.
[0006]
* Method related disadvantages:
-In the case of International Publication WO 95/17453, film production from a dispersion of active chemical substance is itself subject to the stability of the bath containing the dispersion, which is a function of the active substance (eg virucidal) content. Which constitutes a limiting element;
-Similarly, in patent 306,389, the manufacture of controlled size microcapsules requires the use of complex processes, especially with regard to wall thickness and porosity control;
The production of films by either of the above two methods is in each case accompanied by the release of organic vapors; in fact, elastomers are always used in the form of somewhat concentrated solutions in organic solvents.
[0007]
[Problems to be solved by the invention]
As a result of its continued research, the applicant has set a goal to develop a new type of elastomeric material that better meets practical requirements than the level of prior art elastomers, and in particular it has at least one active chemical. In the form of a continuous layer rather than a dispersion or emulsion, thereby causing problems associated with the dispersion and / or emulsification stage (emulsion bath stability, cost of stabilizing polymer, gap Active) only when the material is tornxMakes it possible to obtain a flexible and elastic multilayer material which is particularly suitable for the production of gloves, finger sack or condom.
[0008]
Furthermore, the process for producing the material according to the invention can be carried out in whole or in part in an aqueous medium.
[0009]
[Means for Solving the Problems]
The subject of the present invention is a multilayer polymer film (multilayer material), at least one active chemical comprising a reversible or irreversible gel as a function of temperaturexAt least one layer comprisingA, And synthetic elastomerseAt least two barrier layers comprisingEAnd these layers are said layersAOr layerEPolymeric binder incorporated into at least one ofyAnd / or polymerzIndependent tie layer includingZAnd / or said layerAOr layerEBy at least one chemical or physical treatment.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Chemical treatment is understood to mean either grafting or chemical erosion using acids, such as sulfuric acid, and physical treatment means bombarding the surface of the film with ions or electrons, ie corona or plasma treatment, or photons. That is, it is understood to mean ultraviolet treatment.
[0011]
Gels that are irreversible as a function of temperature are chemically, ie, crosslinkers.I cChemically formed by the addition of (irreversible crosslinkers) and / or by covalent crosslinking, for example by thermal or photochemical activation under the influence of ultraviolet light, but reversible as a function of temperature A typical gel is formed physically, either by hydrogen bonding, van der Waals or dipole-dipole type interactions, or by the formation of crystalline domains or complexes. Such reversible gels may also be cross-linking agents in certain cases.rc(Reversible cross-linking agent).
[0012]
In the case of a reversible gel, the transition occurs at a critical temperature (T-trans) where the physical interaction disappears; the gel-liquid transformation corresponds to this temperature.
[0013]
The layerAAccording to an advantageous embodiment of the invention, when it comprises a reversible gel, the reversible gel is essentially a structural polymer.c, At least one active chemicalxAnd solvents _aFurther comprising a binderyAnd reversible crosslinkersrcCan be included. The combination is a flexible and elastic layerAForm.
[0014]
In certain cases, structural polymerscIs solvents _aAlso works.
[0015]
According to another advantageous embodiment, said reversible gel has a gel-liquid transition temperature (T-trans) of 0 ° C to 120 ° C, preferably 20 ° C to 85 ° C, more preferably 20 ° C to 70 ° C.
[0016]
According to another advantageous embodiment, the layerAThe structural polymer ofcThe elastomereImmiscible with, preferably hydrophilic type, alone or in solvents _aIt is a polymer that is compatible with the active chemicals in solution.
[0017]
According to another advantageous embodiment, the structural polymercIs a synthetic polymer of acrylic or vinyl type, such as polyacrylic acid and polyvinyl alcohol, or of natural origin such as gelatin, gum, pectin, alginate, polypeptide, polyurea, heparinoid and poly (gluconic acid), And cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, or starch derivatives and selected from the group comprising crystallizable or partially crystallizable polymers such as polyethers.
[0018]
According to another advantageous embodiment, the crosslinking agentrc(I) boron derivatives such as boric acid or borax; (ii) divalent metals such as zinc or calcium; and (iii) trivalent metals such as alumina hydrate, aluminum sulfate or water. Selected from the group comprising aluminum in aluminum oxide or chromium in chromium oxide; it is preferably a structural polymer containing hydroxyl functional groups such as polyvinyl alcoholcUsed as a cross-linking agent for structural polymerscIt works by forming physical bonds between the chains.
[0019]
The layerAAccording to another advantageous embodiment, when it comprises an irreversible gel, the latter is essentially a structural polymerc, Cross-linking agentrc, At least one active chemical x and solvents _aFurther comprising a binderyCan be included. As a result, the combination forms a flexible and elastic layer A.
[0020]
In certain cases, structural polymerscEven solvents _aActs as
[0021]
According to another advantageous embodiment, the structural polymercThe elastomereImmiscible with, preferably hydrophilic type, alone or in solvents _aActive chemicals in solution inxIt is a polymer that is compatible with.
According to this advantageous embodiment, the structural polymerc(I) polymers of natural origin, such as gelatin, gums, pectin, alginate, polypeptides, polyureas, heparinoids and poly (gluconic acid), or cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxy Methylcellulose, or starch derivatives, and (ii) synthetic polymers such as polyethyleneimine, polyacrylic acid, polyvinyl alcohol, polyacrylamide and its derivatives, polyvinylpyrrolidone, polydimethyl, which function alone or as an interpenetrated network Selected from the group comprising poly (vinyl ether) such as siloxane or poly (vinyl methyl ether).
[0022]
According to another advantageous embodiment, the crosslinking agenticIs a polymer containing hydroxyl groupscFor example, selected from low or high molecular weight aldehydes or dialdehydes such as glyoxal, or other compounds such as urea-formaldehyde or melamine-formaldehyde derivatives, as well as hydroxyl groups, carboxyl groups or amino groups. For the containing polymer, selected from prepolymers containing isocyanate groups, and generally structural polymerscSelected from any other compound that can chemically react with the compound, such as methacrylate, imide or persulfate.
[0023]
According to the invention the layerAIn addition, whatever the gel is (reversible or irreversible), either a chemical reaction or a physicochemical action, such as a change in surface tension, makes it substantially instantaneous for proteins Active chemicals selected from compounds that can cause various modificationsxAt least one of the following. This type of compound specifically comprises a biocide: said active chemicalxIn order to avoid the possibility of chemical reactions between each other, structural polymerscAnd layerAMust be suitable for different ingredients.
[0024]
As an advantageous combination, the active chemical comprises at least one sequence of quaternary ammonium, preferably dimethyldidecyl ammonium (Bardac®), biguanide, phthalaldehyde, phenol derivative, formaldehyde, polyoxyethylene. Nonionic surfactants, including hexamidine, iodinated compounds such as polyvinylpyrrolidone-iodine complexes, nonionic surfactants with virucidal activity, sodium and potassium dichromate, Sodium and potassium hypochlorites, or eg poly (acrylic acid), poly (divinylbenzyltrimethylammonium chloride), divinyl ether-maleic anhydride copolymer, polyethyleneimine, polyetheramine, polyurea and poly A single or mixture of charged polymers such as polyelectrolytes that exhibit biocidal activity such as peptides.
[0025]
Under certain conditions, active chemicalsxThe solvents _aAlso works.
[0026]
solvents _a(I) a low volatility compound, such as a polyol, preferably ethylene glycol, propylene glycol or glycerol, more specifically a liquid at room temperature and a molecular weight of 62 (ethylene glycol) to 750 daltons (PEG 750) Polyethylene glycol between, or structural polymercWater, (ii) volatile solvents such as low molecular weight alcohols or ketones, non-cyclic or cyclic ether compounds such as tetrahydrofuran, (iii) dimethyl-formamide or dimethyl sulfoxide, or (iv) water ( (Removed by evaporation) alone or in a mixture.
[0027]
Plus layerAIf necessary:
-LayerAAt least one poly A array and layer conforming toEBinders selected from polymers containing both with at least one poly E sequence compatible withyThe polymer comprises a poly-A-block-poly-E type di-block copolymer; a poly-E-block-poly-A-block-poly-E (EAE) type, poly-A-block-poly-E-block-poly-A (AEA) type, poly A-block-poly E-block-poly F (AEF) type or poly A-block-poly F-block-poly E (AFE) type tri-block copolymer; and poly A-graft- Poly E or poly E-graft-poly A type, or poly A-graft-poly E and -poly F type graft copolymers, where the poly F array is a layerAOr layerESelected from the group consisting of acrylic, silicone or polyurethane type adhesives.
[0028]
The poly A sequence is selected from the group consisting of polyoxyethylene, polyvinyl pyridine, poly (acrylic acid), polyvinyl alcohol and quaternary polyvinyl pyridine. The poly E sequence is selected from the group comprising polydienes, polyolefins, polyoxypropylenes and polydimethylsiloxanes.
[0029]
Examples of polydienes or polyolefins include: polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, polystyrene or poly-4-tert-butylstyrene.
[0030]
In particular, graft structures comprising poly A, poly E and poly F sequences include:
-For example, acrylic chain as poly F array
A poly E sequence, for example an alkyl chain, and
-Examples of poly A sequences include polyoxyethylene chains.
[0031]
These structures correspond to certain graft polymers sold under the trademark “Brinoil LE” by the company Coldschmidt.
[0032]
According to another embodiment of the multilayer material, the gel layerAIs:
If the gel is reversibly cross-linked:
-0-98%, preferably 25-98% solvent with respect to the gels _a,
-0.1-74%, preferably 1-74% structural polymer, based on the gelc,
1-80%, preferably 1-74% of said active chemicals relative to the gelxand
-0 to 0.1% crosslinkerrc(Crosslinker content based on total component weight);
When the gel is irreversibly crosslinked:
-0-98%, preferably 25-98% solvent with respect to the gels _a,
-0.1-74%, preferably 1-74% structural polymer, based on the gelc,
1-80%, preferably 1-74% of said active chemicals relative to the gelxand
-0.0001-0.1% crosslinkeric(Crosslinker content based on total component weight).
[0033]
BinderyCan be added at 0.01 to 25% by weight to the gel; solvents _aThe ratio is adjusted accordingly.
[0034]
According to the invention, the multilayer material is a layer.EAs polybutadiene, polyisoprene, acrylic polymer, polychloroprene, polyurethane, chlorobutadiene and copolymers based on methacrylic acid or based on ethylene and vinyl acetate, or SBR (styrene butadiene rubber), SBS (styrene-butadiene) -Synthetic elastomers selected non-limitingly from styrene), SIS (styrene-isoprene-styrene) or SEBS (styrene-ethylene-butylene-styrene) copolymerse, And optionally a binder as defined aboveyincluding.
[0035]
ElastomereIs an organic solvents _eIt can be used either in the form of a medium solution or in the form of an aqueous dispersion (latex).
[0036]
In the present invention, the multilayer material may be a bonding layer.Z(I) di-block, tri-block or graft copolymers as described above (binders)yCopolymers), (ii) for example acrylic or vinyl type polymers such as vinyl acetate or vinyl laurate, (iii) NBR (nitrile-butadiene-rubber), polyurethane and certain polyesters or polyamides Diene polymers containing nitrile functional groups and (iv) layersEA copolymer of the same type as that selected as (the copolymer is a layerAFor compatibility with maleic anhydride treated grafts such as SEBS, or chemically by SBS or SIS chemical erosion using sulfuric acid solutions, or ions or electrons such as corona or plasma treatment Or a polymer selected from the group consisting of (physically treated by impact on the film surface with photons such as UV treatment)zincluding.
[0037]
polymerzIs an organic solvents _zIt can be used either in the form of a medium solution or in the form of an aqueous dispersion (latex).
[0038]
The polymer film or multilayer material is optionally a binder.yAt least one continuous gel layer comprisingAAnd binder as neededyAt least two elastomeric barrier layers comprisingEFormed from the binderyAnd / or independently tie layerZAre used to glue together and exhibit an unexpected flexible and elastic structure that is particularly suitable for the manufacture of gloves, finger sack or condom. The latter may cause the wearer of the material to contaminate the wearer of the material, especially during a medical examination or surgery, or in dentistry, particularly when a break or simple tear in the elastomeric film occurs. In some cases, it provides effective protection against infectious substances transmitted by blood. It is therefore dangerous without the multilayer material of the present invention.
[0039]
Another subject of the invention is at least one layer comprising said reversible gelAAnd synthetic elastomerseAt least two barrier layers containingEA method for producing a multilayer material according to the present invention, wherein the layer comprises the layerAOr layerEPolymer binder incorporated into at least one ofyAnd / or polymerzIndependent tie layer includingZAre held together by:
− “Reversible gel layerAManufacturing Method I includes the following stages:
1) BinderyFirst elastomeric barrier layer with or without supportEThe above polymere(I) aromatic, aliphatic and alicyclic hydrocarbons such as paraffin hydrocarbons, cyclohexane, benzene, toluene, xylene, tetralin or decalin, (ii) petroleum fraction, (iii) other A more polar solvent, such as a low molecular weight alcohol or ketone, (iv) an acyclic or cyclic ether compound, such as tetrahydrofuran, (v) water, or (vi) dimethylformamide or dimethyl sulfoxide, alone or Solvent mixed with two or mores _eAnd dissolve the solution on a suitable substrate,s _eStages produced by evaporating the film; the formation of the film can be accompanied by a crosslinking stage such as, for example, vulcanization. polymereIs used in the form of a dispersion (latex), the solvent is water;
2) At least one layer when the gel is spontaneously formed by physical type bondingAA stage for manufacturing according to the following method;
At least one active chemical substancexA solvent if necessarys _aIn, structural polymercAnd binders as neededyAnd producing a solution by mixing at a temperature higher than the transition temperature T-transform corresponding to the gel-liquid transition (the temperature T-transform is in the range of 20 ° C. to 120 ° C. (the mixture forms a film)); Then
Coating the solution on the layer obtained in stage 1) and cooling to a temperature below the T-transform; film formation is solvents _aCan be accompanied by the release of
3) Layer according to desired orderAAnd layersEApply stages in layers, layersAAnd layersEIs a bonding layer as requiredZAnd separated in layersAAnd layersEIs manufactured according to stages 1) and 2); and
4) BinderyLast elastomeric barrier layer with or without supportEThe solvent_eOr a stage that is manufactured and applied by evaporating water; after this stage, a crosslinking stage such as vulcanization is carried out, if necessary.
[0040]
− “Reversible gel layerAProduction Method II includes the following stages:
1) “Reversible gel layerAThe first elastomeric barrier layer according to stage 1) of process IEStage to manufacture;
2) Crosslinker for reversible gel formationrcWhen addition of at least one layer is requiredAIs produced according to the following method (crosslinking agent)rcThe polymercIntroduced simultaneously with the mixture containing
At least one active chemical substancexA solvent if necessarys _aIn, structural polymercAnd binders as neededyAnd producing a solution by mixing at a temperature higher than the transition temperature T-transform corresponding to the gel-liquid transition (the temperature T-transform is in the range of 20 ° C. to 120 ° C.),
-Structural polymersc, Active chemicalsx,solvents _aAnd binders as neededySimultaneously with the mixture containingrcFor example by spraying (crosslinking takes place rapidly and film formation is induced);
-Applying the solution on the layer obtained in stage 1), then cooling and rapidly crosslinking;
3) Layer according to desired orderAAnd layersEApply stages in layers, layersAAnd layersEIs a bonding layer as requiredZAnd separated in layersAAnd layersEIs manufactured according to stages 1) and 2); and
4) The last elastomeric barrier layer according to stage 1)EA stage to manufacture and apply.
[0041]
− “Reversible gel layerAIs a cross-linking agent in a volatile solvent that itself forms a film in stage 2)rcIncluding the introduction.
[0042]
Another subject of the invention is at least one layer comprising said irreversible gelAAnd synthetic elastomerseAt least two barrier layers containingEAnd the layer is a layerAOr layerEPolymer binder mixed in at least one ofyAnd / or polymerzA method for producing a multilayer material of the present invention that is held together by an independent tie layer Z comprising:
-"Irreversible gel layerAManufacturing Method I includes the following stages:
1) BinderyFirst elastomeric barrier layer with or without supportEA polymer according to the inventioneThe solvents _eAnd dissolve the solution on a suitable substrate,s _eA stage produced by evaporating; cross-linking if necessary;
2) At least one layerAIs produced according to the following method (crosslinking agent)icDirectly into the solution):
At least one active chemical substancexA solvent if necessarys _aIn, structural polymercAnd binders as neededyTo produce a solution,
The resulting solution has a cross-linking agentrcMix directly and
-Applying the solution on the layer obtained in stage 1) (film formation),
-Initiating crosslinking by photochemical and / or thermal routes or by contacting with a crosslinking accelerator;
3) Layer according to desired orderAAnd layersEApply stages in layers, layersAAnd layersEIs a bonding layer as requiredZAnd separated in layersAAnd layersEIs manufactured according to stages 1) and 2); and
4) Last elastomeric barrier layerEIs manufactured and applied according to stage 1).
[0043]
-"Irreversible gel layerAProduction Method II includes the following stages:
1) “Non-reversible gel layer”AThe first elastomeric barrier layer according to stage 1) of process IEStage to manufacture;
2) At least one layerAIs produced according to the following method (crosslinking agent)icAre introduced simultaneously with the mixture);
At least one active chemical substancexA solvent if necessarys _aIn, structural polymercAnd binders as neededyTo produce a solution,
-Polymerc, Active chemicalsx,solvents _aAnd binders as neededyAt the same time as the mixture containingicFor example by spraying (crosslinking takes place rapidly and induces the formation of a film);
-The solution is applied on the layer obtained in stage 1) and then rapidly crosslinked to induce film formation;
3) Layer according to desired orderAAnd layersEApply stages in layers, layersAAnd layersEIs a bonding layer as requiredZAnd separated in layersAAnd layersEIs manufactured according to stages 1) and 2); and
4) Last elastomeric barrier layer according to stage 1)EA stage to manufacture and apply.
[0044]
In the present invention, various active chemical substancesxVarious films manufactured usingABy stacking, the effects of the chemical substances can be obtained at the same time without bonding them.
[0045]
In an advantageous embodiment of the method, a tie layerZIs selected from the group consisting of aromatic, aliphatic and alicyclic hydrocarbons, more polar compounds, for example ethers such as tetrahydrofuran, ketones, dimethylformamide, dimethyl sulfoxide or alcohols and water or mixtures of intermediate polarities. Solvents _ZAbove polymer inzSolvent from solutions _ZAlternatively, it is produced by evaporating water.
[0046]
In this advantageous embodiment, the tie layerZAre photochemically initiated, for example, under the influence of UV radiation and are subjected to thermally or chemically promoted crosslinking, for example by oxidation or using a crosslinking agent. polymerzIs used in the form of a dispersion (latex), the solvent is water.
[0047]
In another form, when the layers are held together by chemical or physical processing, the method of making the multilayer material can be achieved by applying a layer on a suitable substrate.AAnd / or layerEAfter applying the chemical or physical treatment.
[0048]
In other forms, layersAThe multilayer material of the present invention comprising an irreversible gel as a structural polymercOne or more monomersmAnd at least one active chemical substancexFrom a mixture of, by thermal route or by photochemical (ultraviolet irradiation) or radiochemical route (⁶⁰A stage produced by in situ polymerization with a Co cobalt source.
[0049]
In this advantageous form, the mixture further comprises at least one of the following additional components: initiatoriOne or more solventss _a, Thickenerf, Cross-linking agenticOr binderyincluding.
[0050]
In this advantageous form, the monomermAre preferably selected from the group comprising acrylates and their derivatives, such as acrylic acid, hydroxyethyl methacrylate or methyl methacrylate, acrylamide, acrylic amine and their derivatives or vinyl pyrrolidone.
[0051]
In an advantageous embodiment, the number of monomers used is 1 to 10, preferably 1 to 4.
[0052]
According to this alternative aspect:
An initiator if the polymerization is to be initiated thermallyiIs a peroxide family such as benzoyl peroxide, an azonitrile family such as azobisisobutyronitrile, or S₂O₈/ S₂O_FiveSelected from the group consisting of redox pairs like pears;
An initiator if the polymerization is to be initiated photochemicallyiIs selected from the group consisting of an acetophenone family, a benzoin derivative, or a peroxide family.
[0053]
According to another advantageous arrangement of this embodiment, the thickenerfAre aluminum stearates, calcium linoleate pastes, soap solutions, hydrogenated castor oils, triglycerides, bentonite type modified clays, polyol esters, silicas, and monomer mixtures It is selected from the group consisting of polymers that are compatible or have the same properties as gelled polymers such as modified poly (acrylic acid) s, polymethacrylates or polyvinylpyrrolidone.
[0054]
Another subject of the invention is the elastomer according to the invention as a coating for a substrate, in particular an elastomer or plastic substrate (gloves, finger sack, condom, etc.) or overforming a rubbing seal. There are various applications of film.
[0055]
In addition to the preceding arrangements, the present invention encompasses other arrangements that will become apparent from the following description, which refers to the method embodiments and the accompanying drawings that are the subject of the present invention. .
[0056]
1 to 4 illustrate various aspects of the multilayer material of the present invention.c,e,x,ic,rc,s _a,s _e ,s _z,yas well aszHas the following meaning:c; Structural polymerc;e: Elastomere;x: Active chemical substancesx;rc: Reversible cross-linking agent;ic: Irreversible cross-linking agent;y: Bindery;z: A polymer that provides adhesion between two layers of different structurez, And parentheses mean that the substance is an optionally present component.
[0057]
FIG. 5 shows a polymer that allows the preparation of a flexible and elastic layerc, Active substancexAnd solvents _aMixture combination (ternary diagram: describing the limits of the range of gels present): CrosslinkerrcIn this figure, the shaded area corresponds to the claimed composition range.
[0058]
-And Figure 6 shows as an example a combination (ternary diagram) of ethylene glycol, Bardac (dimethyldidecylammonium) and gelatin, which allows the preparation of a flexible and elastic layer at room temperature. Describes the range in which the gel exists. In this figure, the portion further enclosed by diagonal lines corresponds to the scope of the claims.
[0059]
However, it should be clearly understood that these examples are provided only for the purpose of illustrating the subject matter of the present invention and do not constitute any limitation.
[0060]
According to the present invention, a laminated multilayered polymeric film is shown without being limited to one of the following structures.
[0061]
-LayerAHas two layersEA three-layer polymeric film sandwiched between the two (FIG. 1).
[0062]
-LayerE,layerZ,layerA,layerZAnd layersE5 layer polymeric film (FIG. 2) containing continuously.
[0063]
-LayerE,layerA1,layerA2,layerA3And layersE5 layer polymeric film (FIG. 3) containing continuously.
[0064]
-LayerE,layerZ,layerA1,layerZ,layerA2,layerZ,layerA3,layerZAnd layersE9-layer polymeric film (FIG. 3).
[0065]
-LayerE,layerA1,layerE,layerA2,layerE,layerA3And layersEIs a seven-layer polymeric film (FIG. 4).
[0066]
-LayerE,layerZ,layerA1,layerZ,layerE,layerZ,layerA2,layerZ,layerE,layerZ,layerA3,layerZAnd layersEIs a 13-layer polymeric film (FIG. 4).
[0067]
In all these structures, the layerAAnd layersEIs a binderyOptionally containing one layerAIs also a cross-linking agentrcOricMay be included arbitrarily (in the figure, each (y), (ic)as well as(rc)).
[0068]
layerA1,layerA2And layersA3The same active chemicalxAt different concentrations, or alternatively, active chemicals of different propertiesxMay be included.
[0069]
The invention will now be described by way of examples, but in addition to becoming apparent from the following, the invention is in no way limited to the implementations, examples and forms of application as set forth herein. On the other hand, including all variations thereof that would occur to those skilled in the art without departing from the context or scope of the present application.
[0070]
【Example】
Example 1:  Reversibly cross-linked layerAPreparation of
Gelatin produced from collagen by acid treatment and having a Bloom value of 175 is commercially available from Lonza under the name didecyldimethylammonium chloride (“Bardac® 2270E”): Bardac) and ethylene glycol (or water) containing 10% by weight Bardac® with respect to the gel are dissolved at 60 ° C. with stirring.
[0071]
The clear solution formed contains 15% gelatin by weight.
[0072]
The temperature of the mixture (60 ° C.) corresponds to a temperature higher than the gel-liquid transition temperature. This transition temperature is determined by a sudden change in the viscosity of the mixture at that temperature, in this case 30-35 ° C.
[0073]
the filmAThe solution is cooled at a predetermined condition in the form of a film at 50 ° C. using a film drawer having a controlled thickness of 100 μm, or a ceramic foam according to a dipping method. This solution is obtained by cooling on a ceramic former.
[0074]
The film thus obtainedAHas good elasticity and flexibility and keeps Bardac® properly.
[0075]
Example 2:  Reversibly cross-linked layerAPreparation of
The preparation is carried out in the same way as in Example 1, except that the relative proportions of the other components are the same, except that the proportion of Bardac® is varied between 5% and 25% with respect to the gel.
[0076]
[Table 1]

[0077]
In all cases, after film formation, cooling to a temperature below Ttrans yields an elastic and flexible gel that properly holds the virucidal agent.
[0078]
These compositions are consistent with the ternary diagrams of FIGS. 5 and 6 obtained by measuring at 25 ° C.
[0079]
Example 3:  Reversibly cross-linked layerAPreparation of
The preparation is carried out in the same manner as in Examples 1 and 2, except that Burdak® is replaced with a polyvinylpyrrolidone-iodine complex commercially available from Aldrich under reference number 86,056-5.
[0080]
The polyvinylpyrrolidone-iodine complex is dissolved in a mixture of water and gelatin with stirring at 60 ° C. so that a 5% by weight polyvinylpyrrolidone-iodine complex solution is obtained.
[0081]
The clear solution formed contains 15% gelatin by weight.
[0082]
The temperature of the mixed liquid (60 ° C.) corresponds to a temperature higher than the gel-liquid transition temperature. This transition temperature is determined by a sudden change in the viscosity of the mixture at that temperature, in this case 30-35 ° C.
[0083]
the filmAIs prepared while cooling the solution at 50 ° C. using a film drawer having a controlled thickness of 100 μm under the predetermined conditions of filming.
[0084]
The film thus obtainedAHas good elasticity and flexibility and keeps the virucidal agent properly.
[0085]
Example 4:  Reversibly cross-linked layerAPreparation of
In this example, the structural polymercIs polyacrylamide (PAAm) sold under the name N 300 by Cytec. Dissolve PAAm with stirring to a 0.1-0.5% solution in water. the filmAIs obtained after evaporating the water on a ceramic former. The resulting film has good elasticity.
[0086]
Example 5:  Reversibly cross-linked layerAOf three-layer multilayer material with
This example shows two barrier layersELayer inserted betweenAIt relates to the preparation of a simple multilayer material consisting of
[0087]
Polyisoprene (PI) is dissolved with stirring in cyclohexane to give a 15% by weight PI-containing solution.
[0088]
Using a film drawer with a controlled thickness of 200 μm, coating the glass material with an elastomeric cyclohexane solution, a 60 μm thick layerETo prepare. Two steps are required to do this. A cyclohexane solution containing 15% polyisoprene is used.
[0089]
This layer is a 50 μm layer containing Bardac®, gelatin and ethylene glycol in a ratio of 0.5 / 2/10 prepared according to the same process described in Example 1 or 2.AIs added.
[0090]
Then the layerAOn top of the second 60 μm thick elastomer barrier layerEIs prepared.
[0091]
Example 6:  Reversibly cross-linked layerAPreparation of
In this example, the structural polymercIs a Mowiol® 26-88 type polyvinyl alcohol (PVA) characterized by a hydrolysis rate of 88% and a viscosity of 26 mPa.s for a 4% aqueous solution at 20 ° C.
[0092]
Mowiol® is dissolved in a water / PEG mixture under stirring at 80 ° C. to obtain a 7.5% Mowiol® solution. Bardac® is added to contain 76.5% in this solution.
[0093]
the filmACan be obtained by dipping a ceramic former in the solution and evaporating the water at 70 ° C. The resulting film has good elasticity.
[0094]
Example 7:  Reversibly cross-linked layerAOf multi-layered material containing 5 layers
This example shows two barrier layersELayer inserted betweenAMade of adhesive bond layerZRelates to the preparation of a multilayer material, which is improved by
[0095]
By immersing the former in a cyclohexane solution containing 15% PI, as in Example 5, the layerETo prepare. This layer is composed of SEBS treated with maleic anhydride, diluted with cyclohexane to contain 15% SEBS and sold under the name Kraton 1901 (Shell). Add to. After evaporating the solvent, the same layer as in Example 6AIs obtained by dipping. The tie layer and then the final elastomer layer are prepared as described above.
[0096]
Example 8:  Reversibly cross-linked layerAOf multi-layered material containing 5 layers
The preparation is carried out in the same manner as in Example 7 except that SEBS treated with maleic anhydride is replaced with a toluene solution containing 3% of acrylic acid / ethylene copolymer. The copolymer is sold under the name Vamac® from Dupont or under the name ATX® from Exxon.
[0097]
Example 9:  Reversibly cross-linked layerAOf multi-layered material containing 5 layers
The preparation was carried out in the same manner as in Example except that SEBS treated with maleic anhydride was replaced with a toluene solution containing 3% of a methacrylate / styrene copolymer sold under the name Cyrolite® G20 by Huls. Same as 7.
[0098]
Example 10:  Reversibly cross-linked layerAOf three-layer multilayer material containing
This example shows two barrier layersELayer inserted betweenAMade of adhesive layerAInside binderyRelates to the preparation of multilayer materials which are improved by
[0099]
A first elastomer layer is obtained in the same manner as in the above example. A layer of 3% butadiene-styrene-maleic anhydride copolymer sold under the name SMA 1440H by the company Elf Atochem.AAdd to the solution used to make Second barrier layerEIs obtained as described above.
[0100]
Example 11:  Reversibly cross-linked layerAAnd bonding layerZ5 layer multilayer material with
This example shows two barrier layersEIt relates to the preparation of a multilayer material consisting of an A layer inserted between the layers, in which the adhesion between the layers is improved by the bonding layer Z.
[0101]
Similar to Example 5, 60 μm thick layerEIs prepared by coating the glass material with an elastomeric cyclohexane solution using a film drawer having a controlled thickness of 200 μm. To do this, two steps are required. A cyclohexane solution containing 15% polyisoprene is used.
[0102]
This layer is packaged from Rohm & Haas with a film drawer having a thickness of 50 μm in the form of a dispersed aqueous solution having a solid content of 55% and Primal EP 6010 Add a tie layer made of acrylic latex, sold under the name K.
[0103]
After evaporating water at 50 ° C. to form a tie layerAIs applied at 50 ° C. using a film drawer having a thickness of 50 μm and then cooled until a flexible and elastic film is formed.
[0104]
Finally, a 50μ thick tie layerZAnd then the final elastomer layer with a thickness of 60μEIs prepared as described above.
[0105]
The resulting multilayer material contains 5 layers and exhibits acceptable resilience, acceptable flexibility, and acceptable adhesion between inner layers.
[0106]
Example 12:  Reversibly cross-linked layerAAnd layersEBinder mixed inyOf three-layer multilayer material with
This example shows two barrier layersELayer inserted betweenAThe adhesion between these layers consists of layersEBinders put intoyRelates to the preparation of multilayer materials which are improved by
[0107]
Polyisoprene (PI) is dissolved in cyclohexane with stirring so as to be a 15% by weight PI-containing solution.
[0108]
To this solution is added a polybutadiene-block-polyoxyethylene di-block copolymer having a molecular weight of 51,500 daltons and containing 20% of one mole of polyoxyethylene constituent to obtain a solution containing 5% of the copolymer. (Expressed in mass with respect to complete solution).
[0109]
60 μm thick filmEIs obtained as described in Example 5 by evaporating the solvent at 50 ° C.
[0110]
50 μm thick layerAThen 60 μm thick layerEIs prepared as described in Example 11 above.
[0111]
The multilayer material includes three layers and exhibits acceptable resilience, acceptable flexibility and acceptable adhesion between layers.
[0112]
Example 13:  Reversibly cross-linked layerAHave a layerABinder mixed inyMethod for the preparation of a three-layer multilayer material having
Preparation layered binderAThe procedure is the same as that in Example 12 except that the method is used.
[0113]
Gelatin derived from collagen by acid treatment and having a Bloom value of 175 in a mixture of Bardac® and ethylene glycol containing 10% by weight Bardac® with respect to the gel, 60% Dissolve under stirring at ° C.
[0114]
The clear solution formed contains 15% gelatin by weight.
[0115]
To this solution is added a graft copolymer containing the composition of polyoxyethylene and acrylic chains on the alkyl backbone, sold under the name Brinoil® LE 2362 by Goldschmidt AG. .
[0116]
The final solution contains 5% graft copolymer with respect to the gel.
[0117]
By cooling this solution using a film drawer having a controlled thickness of 50 μm at 50 ° C., pre-conditioned to film, layerAGet.
[0118]
layerA60 μm thick layer on both sidesEIs prepared in a manner similar to that shown in Example 11.
[0119]
Example 14:  Two layers with two different virucidal agents and reversibly cross-linkedAAnd bonding layerZOf a six-layer multilayer material having
60μm thick elastomer layerEAnd then a bonding layer with a thickness of 50 μmZIs prepared analogously to Example 11.
[0120]
Then a first 50 μm thick layerAAdd The layerAIs the active chemical substance described in Example 1xAs a mixture containing Bardac (registered trademark).
[0121]
Second layer, also 50 μm thickATo prepare. The layerAIs active chemical according to Example 3xAs a mixture containing a polyvinylpyrrolidone-iodine complex.
[0122]
This second layer is then used as described in Example 11.A50 μm bonding layerZThen the last elastomer layerEIs added.
[0123]
The multilayer material thus obtained exhibits an acceptable elasticity, an acceptable flexibility and an acceptable interlayer adhesion.
[0124]
Example 15:  Reversibly cross-linked layerAAnd have a layerABinder mixed intoyOf three-layer multilayer materials prepared by a "fully aqueous" process containing
The preparation was done by replacing the polyisoprene solution in cyclohexane with a prevulcanized natural rubber latex sold under the name Revultex LA, containing 60.5% solids content. This is performed in the same manner as in Example 13.
[0125]
Its viscosity is 70 mPa.s at 20 ° C.
[0126]
90 μm thick layerEIs prepared by coating a glass material with a pre-vulcanized latex using a film drawer having a controlled thickness of 150 μm.
[0127]
layerEAfter evaporating water from the elastomer latex and vulcanizing at 60 ° C., the layerAIs applied as described in Example 13 and then the last layerETo prepare.
[0128]
The multilayer material thus obtained exhibits an acceptable elasticity, an acceptable flexibility and an acceptable adhesion between the inner layers.
[0129]
Example 16:  Reversibly cross-linked layerAHaving a binderZOf a five-layered multi-layered material having a complete and prepared by an aqueous process
The preparation is carried out as in Example 11 using a pre-vulcanized natural rubber latex, Rebretex® LA.
[0130]
90μm thick layerEIs prepared by coating a glass material with a pre-vulcanized latex using a film drawer having a controlled thickness of 150 μm.
[0131]
layerEAfter evaporating water from the elastomer latex and vulcanizing at 60 ° C., a 50 μm thick tie layer made of acrylic latex (primal EP60-10 type)ZAre applied as described in Example 7.
[0132]
Next, a 50 μm thick layerAAdd The layerAIs the active chemical substance described in Example 1xA mixture containing Bardac (registered trademark) is used.
[0133]
Finally, a 50 μm thick tie layerZAnd then the last elastomer layer of 90 μm thicknessEIs prepared as described above.
[0134]
The multilayer material thus obtained exhibits acceptable elasticity, acceptable flexibility and acceptable interlayer adhesion.
[0135]
Example 17:  Layer cross-linked by gamma irradiationAOf three-layer multilayer material containing
An 8% aqueous PVP solution is prepared and poured between 1 mm intervals between two glass plates. This system has a strength of 0.66 rad / min⁶⁰Place it 31.5 cm away from the Co source for one month. The gel thus obtained has good flexibility.
[0136]
Example 18:  Irreversibly cross-linked layerAOf three-layer multilayer material containing
This example shows two barrier layersELayer inserted betweenAThe layerARelates to the preparation of multi-layer materials, which are crosslinked.
[0137]
A first elastomer layer is obtained as in Example 5. 3% glutaraldehyde with the layer described in Example 1AAdd to. Second barrier layerEIs obtained as described above.
[0138]
Example 19:  Irreversibly cross-linked layerAOf three-layer multilayer material containing
This example shows two barrier layersELayer inserted betweenAThe layerARelates to the preparation of multi-layer materials, which are crosslinked.
[0139]
A first elastomer layer is obtained in the same manner as in the above example. layerAWas obtained by dipping in a solution containing Bardac®, gelatin and ethylene glycol in the same manner as in Example 1, and then the former was immersed in an acetone solution containing 3% glutaraldehyde. Immerse. After evaporation, the former is again immersed in the elastomer solution.
[0140]
Example 20:  Irreversibly cross-linked layerAPreparation of
In this example, the structural polymercIs a Mowiol® 28-99 type polyvinyl alcohol characterized by a molecular weight of 88,000 daltons and a hydrolysis rate of 99%. Its viscosity is 28 mPa.s in a 4% aqueous solution at 20 ° C.
[0141]
Mowiol® is added to water (solvent) so that a 2.5% Mowiol® solution is obtained at 80 ° C. with stirring.s _a).
[0142]
To this solution, Triton X100® (active chemical x) is added with stirring until a clear solution containing 10% Triton (expressed in terms of Mowiol® solution) is obtained.
[0143]
The clear solution obtained is provided in the form of a viscous liquid.
[0144]
Irreversible crosslinkericIs prepared by mixing glutaraldehyde in a water / hydrochloric acid mixture containing 9 parts water per part hydrochloric acid on a molar basis so that the solution contains 0.005% glutaraldehyde.
[0145]
layerAIs prepared by spraying 10 parts by weight of Mowiol® containing solution simultaneously with 0.0475 parts by weight of irreversible crosslinker containing solution.
[0146]
Layers prepared in this wayAIndicates acceptable elasticity and acceptable flexibility.
[0147]
Example 21:  Irreversibly cross-linked layerAIncluding an elastomer layer that adheres between its inner layersEOf three-layer multilayer material obtained by processing of
This example shows two barrier layersELayer inserted betweenAIt relates to the preparation of multilayer materials, whose adhesion is obtained by chemical treatment of the elastomeric layer.
[0148]
The elastomer layer is prepared by immersing the ceramic former in a cyclohexane solution containing 15% styrene-isoprene-styrene (SIS) (or styrene-butadiene-styrene (SBS)) copolymer. After evaporation of the solvent, the former is immersed in a 25 g / l aqueous solution of Oniachlor® (sold by Bostik) for 5 minutes.
[0149]
Excess product can be removed by rinsing with ultrapure water. Then layerAIs obtained in the same manner as in Example 6. The last elastomer layer is added as in Example 5.
[0150]
Layer adhesion is acceptable.
[0151]
Example 22:  Irreversibly cross-linked layerAOf three-layer multi-layered materials that are interpenetrated networks that penetrate each other
First elastomer layerEIs obtained in the same manner as in the above example. The preparation is performed in the same manner as in Example 1 with respect to dissolving gelatin. Then, AAm, N, N'-bisacrylamide, AAm crosslinkeric, Redox initiator I and crosslinker for gelatinic 'Glutaraldehyde is added to the solution. The former is then immersed in this solution containing Bardac®. After the water has evaporated, it is covered with a SEBS layer as described above.
[0152]
Example 23:  layerAOf a three-layer multilayer material, which is obtained by in situ polymerization
Elastomer layerEIs prepared as in Example 5. layerAIs prepared by immersing the former in a mixed solution containing hydroxyethyl methacrylate (HEMA), polyethylene glycol having a mass of 400 and Bardac (registered trademark) in a ratio of 1/1/1. Furthermore, the polymerization is carried out with Na_ThreeS_ThreeO_FiveAnd (NH_Four)₂S₂0₈In the presence of The final elastomer layer is added as in Example 5.
[0153]
Example 24:  layerAIs a cross-linking agenticOf a three-layer multilayer material obtained by in situ polymerization in the presence of water
Elastomer layerEIs prepared analogously to Example 5. 0.3% ethylene glycol dimethacrylate (expressed by the mass of the polymer) as a crosslinkericTo the mixture described in Example 23.
[0154]
The polymerization is started at 70 ° C. in the presence of AIBN.
[0155]
Second elastomeric barrier layerELayer by the dipping method (dipping method) described in Example 5APrepare above.
[0156]
Example 25:  layerAIs a cross-linking agenticOf a three-layer multilayer material obtained by in situ polymerization in the presence of
Elastomer layerEIs prepared as in Example 5. layerAAdd The layerAAcrylamide, ethylene glycol, water, cross-linking agenticAs a mixture containing N, N'-bisacrylamide (NBAAm) and Burdac (R) as
In accordance with Example 6. The polymerization is initiated at room temperature in the presence of a redox initiator.
[0157]
Second elastomeric barrier layerELayer by the dipping method described in Example 5APrepare above.
[0158]
Example 26:  layerAThickenerfOf a three-layer multilayer material obtained by in-situ polymerization in the presence of
Elastomer layerEIs obtained by immersion in a polychloroprene latex solution.
[0159]
0.5% silica, thickenerfTo the mixture of Example 23. The polymerization is started at 70 ° C. in the presence of benzoyl peroxide.
[0160]
Second elastomeric barrier layerELayer by immersing the former in a 15% polyurethane solutionAPrepare above.
[0161]
Example 27:  layerAThickener with the same chemical properties as gelfOf a three-layer multilayer material obtained by in-situ polymerization in the presence of
[0162]
Barrier layerEIs obtained by the same method as in Example 5. A layer containing PHEMA containing HEMA, Bardac® and PEG in a ratio of 3/1/1 according to the same conditions as in Example 23, and pre-synthesized in large quantities in the presence of BPAThe layer by the same wayEAdd to.
[0163]
The last elastomer layer is added as in Example 5.
[0164]
Example 28:  layerAThickenerfIn the presence of and adhesive layersZOf a 5 layer multilayer material, obtained by in situ polymerization in the presence of
[0165]
Barrier layerEIs obtained by the same method as in Example 5. The former is immersed in a Vamac solution and then HEMA, Bardac®, PEG, BP (benzoyl peroxide) and Modarez 200 (Modarez 200) in a ratio of 2/1/1 according to the conditions of Example 23. D) in a solution containing poly (acrylic acid) sold by the company Protex.
[0166]
After polymerization, remove the former as described above in the elastomer solution.EImmerse in.
[0167]
Example 29:  layerAIs obtained by in-situ polymerization and has an adhesive layerZOf a 5 layer multilayer material containing
[0168]
Barrier layerEIs obtained by the same method as in Example 5. A tie layer made of an acrylic resin latex sold under the name Primal EP 6010K is applied in the same manner to the layer.EAdd to. After drying, the layerAAre attached by a dipping method. It is obtained by mixing methyl methacrylate 0-50% with hydroxyethyl methacrylate 100-50% in the presence of water, Bardac® and PEG 400.
[0169]
Initiation is performed with BP at 70 ° C. After obtaining the gel, the second barrier layer described in Example 5EThe former is again immersed in the primal solution before coating with.
[0170]
Example 30:  layerAOf a three-layer multilayer material, which is obtained by in-situ polymerization initiated by UV irradiation.
[0171]
Barrier layerEIs obtained by the same method as in Example 5. The HEMA / NVP (N-vinylpyrrolidone) (70/30) mixture was prepared in the same manner by using the initiator.i, 2-hydroxy-2,2-dimethylacetophenone (Darocur 1173) and solvents _a In the presence of glycerol, layerEAdd to.
[0172]
Polymerization is initiated by UV irradiation (λ = 365 nm) for 2 hours. After obtaining the gel, remove the former as described above in the elastomer solution.EImmerse in.
[0173]
Example 31:  layerAAre irreversibly cross-linked and the adhesion between the interlayers is the elastomer layerEPreparation of a four-layer multilayer material that was imparted by the treatment of
[0174]
This example shows two barrier layersELayer inserted betweenAWith respect to the preparation of a multilayer material composed ofEThe other surface is provided by the adhesive layer Z.
[0175]
Elastomer layerEIs obtained by immersing the ceramic former in 15% SBS or SIS solution according to Example 5.
[0176]
The former is placed in a chamber through which ionized nitrogen, argon or oxygen gas passes to oxidize the surface. By improving the wettability of the elastomer, the adhesion with the layer obtained in the same manner as in Example 5 is improved. The former is then immersed in a solution consisting of gelatin, Bardac® and ethylene glycol (as described in Example 5) and then in an acetone solution containing 0.3% glutaraldehyde, and the elastomer as described above. layerECover with.
[Brief description of the drawings]
FIG. 1 shows an embodiment of a multilayer material according to the present invention, a layerAHas two layersEIt is a figure which shows the three-layer polymeric film pinched | interposed between.
FIG. 2 shows one embodiment of the multilayer material of the present invention, a layerE,layerZ,layerA,layerZAnd layersEIt is a figure which shows the 5-layer polymeric film which contains continuously.
FIG. 3 shows embodiments and layers of the multilayer material of the present invention.E,layerA1,layerA2,layerA3And layersE5 layer polymeric film or layer continuously containingE,layerZ,layerA1,layerZ,layerA2,layerZ,layerA3,layerZAnd layersEIt is a figure which shows the 9-layer polymeric film which contains continuously.
FIG. 4 shows embodiments and layers of the multilayer material of the present invention.E,layerA1,layerE,layerA2,layerE,layerA3And layersE7-layer polymeric film or layer continuously containingE,layerZ,layerA1,layerZ,layerE,layerZ,layerA2,layerZ,layerE,layerZ,layerA3,layerZAnd layersEIt is a figure which shows the 13-layer polymeric film which contains continuously.
FIG. 5 Polymerc, Active substancexAnd solvents _a3 shows a ternary diagram showing a combination of mixtures. In this figure, the shaded area corresponds to the claimed composition range.
FIG. 6 is a three-component diagram showing a combination of ethylene glycol, Bardac (registered trademark) (dimethyldidecyl ammonium) and gelatin as an example. In this figure, the portion further enclosed by diagonal lines corresponds to the scope of the claims.

Claims (41)

Comprising at least one layer A comprising a gel that is reversible or irreversible as a function of temperature and carrying at least one active chemical substance x , and at least two barrier layers E comprising a synthetic elastomer c , By a polymeric binder y incorporated in at least one of layer A or layer E and / or by an independent bonding layer Z comprising a polymer z and / or at least one chemical or physical of said layer A or layer E A multilayer polymer material, wherein the layers are integrally held by treatment. The multilayer material according to claim 1, characterized in that when the layer A comprises a reversible gel, the latter essentially comprises _a structural polymer c , at least one active chemical x and a solvent sa . The multilayer material according to claim 2, characterized in that the reversible gel further comprises at least one of the following products: binder y and reversible cross-linking agent rc . The reversible gel exhibits a gel-liquid transition temperature (T-trans) between 0 ° C. and 120 ° C., preferably between 20 ° C. and 85 ° C., more preferably between 20 ° C. and 70 ° C. The multilayer material according to any one of claims 1 to 3. Claim structural polymer c of the layer A, characterized in that a is preferably a polymer that is immiscible with the synthetic elastomer e is and and active chemical substances x and / or solvent s _a compatible hydrophilic type 1 The multilayer material in any one of -4. The structural polymer c is a synthetic polymer of acrylic or vinyl type or a polymer of natural origin such as gelatin, gum, pectin and alginate, polypeptide, polyurea, heparinoid and poly (gluconic acid), as well as methylcellulose, hydroxyethylcellulose, 6. A cellulose derivative, such as hydroxypropylcellulose and carboxymethylcellulose, or a starch derivative and a group comprising a crystallizable or partially crystallizable polymer. A multilayer material according to any one of the above. The cross-linking agent rc is (i) certain boron derivatives such as boric acid or borax; (ii) certain divalent metals such as zinc or calcium; and (iii) alumina hydrate, aluminum sulfate or certain aluminum. 7. Multilayer material according to any of claims 3 to 6, characterized in that it is selected from the group consisting of certain trivalent metals such as aluminum in hydroxide or chromium in chromium oxide. 2. The layer A according to claim 1, characterized in that when the layer A comprises an irreversible type gel, the latter essentially comprises _a structural polymer c , a cross-linking agent ic , at least one active chemical substance x and a solvent sa. The multilayer material described. The multilayer material according to claim 8, wherein the irreversible gel further comprises a binder y . Said structural polymer c of layer A is (i) a polymer of natural origin such as gelatin, gum, pectin and alginate, polypeptide, polyurea, heparinoid and poly (gluconic acid), or methylcellulose, hydroxyethylcellulose, hydroxy Certain cellulose derivatives such as propylcellulose and carboxymethylcellulose, or certain starch derivatives, and (ii) polyethyleneimine, poly (acrylic acid), polyvinyl alcohol, polyacrylamide and its derivatives, polyvinylpyrrolidone, polydimethylsiloxane or poly ( Characterized in that it is selected from the group consisting of synthetic polymers such as poly (vinyl ether), such as vinyl methyl ether), these single or interpenetrating networks Multilayer material according to Motomeko 8 or claim 9. The crosslinker ic for layer A is selected from other compounds such as low or high molecular weight aldehydes or dialdehydes such as glyoxal, urea-formaldehyde or melamine-formaldehyde derivatives, for polymers c containing hydroxyl groups. And a polymer containing hydroxyl groups, carboxyl groups or amino groups, selected from prepolymers containing isocyanate groups, or from methacrylates, imides or persulfonates. . Substantially instantaneous denaturation of proteins when the active chemical x present in the layer A is simply contacted, for example by either chemical reaction or physicochemical action such as modification of surface tension The multilayer material according to any one of claims 1 to 11, which is selected from compounds capable of causing 13. The multilayer material according to claim 12, wherein the chemical substance x is selected from biocides. The biocide is quaternary ammonium, preferably dimethyldidecyl ammonium, biguanide, phthalaldehyde, phenol derivative, formaldehyde, a nonionic surfactant comprising at least one sequence of polyoxyethylene, hexaamidine , Iodinated compounds such as polyvinylpyrrolidone-iodine complexes, nonionic surfactants with virucidal activity, sodium and potassium dichromate, sodium and potassium hypochlorite, or poly (acrylic acid) Such as poly (divinylbenzyltrimethylammonium chloride), divinyl ether-maleic anhydride copolymer, polyelectrolytes exhibiting biocidal activity such as polyethylenimine, polyetheramine, polyurea and polypeptides. 14. A multilayer material according to claim 12 or claim 13, wherein the multilayer material is selected from the group consisting of limers, alone or as a mixture. The solvent s _a for the layer A is, (i) a polyol, preferably ethylene glycol, propylene glycol or glycerol, more generally, a liquid molecular weight at room temperature 62 from (ethylene glycol) 750 daltons (PEG 750 Or a low volatility compound such as water if the structural polymer c contains water, and (ii) a low molecular weight alcohol or ketone, an acyclic or cyclic ether compound, dimethylformamide, 9. Multilayer material according to claim 2 or 8, characterized in that it is selected from the group consisting of dimethyl sulfoxide or a volatile solvent such as water, alone or in a mixture. Poly-A-Block-Poly-E type di-block wherein binder y comprises both at least one poly A array compatible with layer A and at least one poly E array compatible with layer E Copolymer, poly E-block-poly A-block-poly E (EAE) type, poly A-block-poly E-block-poly A (AEA) type, poly A-block-poly E-block-poly F (AEF) ) Type or poly A-block-poly F-block-poly E (AFE) type tri-block copolymer, and poly A-graft-poly E or poly E-graft-poly A type, or poly A-graft-poly E and - a polymer selected from the group consisting of poly F type graft copolymers (where poly F sequence is compatible with the layer a or the layer E) Alternatively, the multilayer material according to claim 1, characterized in that selected acrylic, silicon or polyurethane type of adhesive. The poly A sequence is selected from the group consisting of polyoxyethylene, polyvinyl pyridine, poly (acrylic acid), polyvinyl alcohol and quaternary polyvinyl pyridine, and the poly E sequence consists of polydiene, polyolefin, polyoxypropylene and polydimethylsiloxane. The multilayer material according to claim 16, wherein the multilayer material is selected from the group. When the gel layer A is reversibly cross-linked:
- 0 to 98% relative to the gel, preferably 25 to 98% of solvent s _a,
0.1 to 74%, preferably 1 to 74% structural polymer c , based on the gel,
1 to 80%, preferably 1 to 74% of the active chemical x and 0 to 0.1% of the crosslinker rc (crosslinker content is based on the total component weight)
The multilayer material according to claim 1, comprising: When the gel layer A is irreversibly crosslinked, the gel:
- 0 to 98% relative to the gel, preferably 25 to 98% of solvent s _a,
0.1 to 74%, preferably 1 to 74% structural polymer c , based on the gel,
Contains 1 to 80%, preferably 1 to 74% of the active chemical x, and 0.0001 to 0.1% of a crosslinker ic (crosslinker content based on total component weight) A multilayer material according to any one of claims 1 and 8-11. The gel layer A comprises additionally a binder y, is from 0.01 to 25% by weight of the binder y is with respect to the gel, and wherein the ratio of solvent s _a are adjusted consequently 20. A multilayer material according to claim 18 or claim 19. The elastomer layer E is polybutadiene, polyisoprene, acrylic polymer, polychloroprene, polyurethane, copolymers based on chlorobutadiene and methacrylic acid or copolymers based on ethylene and vinyl acetate, or SBR (styrene butadiene rubber), SBS (styrene). 18. A binder according to claim 16 or 17, comprising a synthetic elastomer e selected from -butadiene-styrene), SIS (styrene-isoprene-styrene) or SEBS (styrene-ethylene-butylene-styrene) copolymers, optionally. The multilayer material according to claim 1, comprising y . The polymer z of the tie layer Z is (i) a di-block, tri-block or graft copolymer according to claim 16, (ii) an acrylic or vinyl type polymer, (iii) eg NBR (nitrile-butadiene-rubber ), A nitrile group-containing diene polymer such as polyurethane and certain polyesters or polyamides and (iv) selected from the group consisting of copolymers of the same type as those selected as layer E , in order to make them compatible with layer A The multilayer material according to claim 1, wherein the multilayer material is chemically treated by grafting or chemical erosion with an acid solution, or physically by bombardment of the film surface with ions, electrons or photons. A process for producing a multilayer material comprising at least one layer A comprising a reversible gel according to claim 1, characterized in that it comprises the following stages:
1) an initial elastomeric barrier layer E , with or without a binder y, and the polymer e according to claim 21 with (i) aromatic, aliphatic and alicyclic hydrocarbons such as paraffin hydrocarbons, cyclohexane Benzene, toluene, xylene, tetralin or decalin, (ii) petroleum fractions, (iii) other more polar solvents such as low molecular weight alcohols or ketones, (iv) acyclic or cyclic ether compounds, (v) Dissolve in water or (vi) s _e selected from the group consisting of dimethylformamide or dimethyl sulfoxide alone or a mixture, apply the solution onto a suitable substrate, evaporate the solvent s _e and crosslink as necessary. Stage to be manufactured by;
2) when the gel spontaneously forms by physical type bonding, the stage in which at least one layer A is produced according to the following method;
In the range of 20 ° C. to 120 ° C., which corresponds to the liquid transfer - - at least one active chemical substance x, with optionally a solvent s _a, a binder y optionally and structural polymer c, gel After producing a solution by mixing at a temperature higher than the transition temperature (T-trans),
Applying the solution onto the layer obtained in stage 1) and cooling to a temperature below the T-transform;
3) stage for applying the layers A and E in the order according to the desired order, layers A and E are separated by bonding layers Z optionally and in accordance with the layer A and the layer E is stage 1) and 2) is produced; and 4) the stage of making and applying the final elastomer barrier layer E carrying no or carries a binding agent y by evaporating the solvent s _e or water; after this stage, crosslinking optionally stage To implement. A method for producing a multilayer material comprising at least one layer A comprising a reversible gel according to claim 1, characterized in that it comprises the following stages:
Applying a first elastomeric barrier layer E, which 1) does not carry or carries a binding agent y, the polymer e of claim 21 is dissolved in a solvent S _e of claim 23, the solution on a suitable substrate and evaporated the solvent s _e; stage that prepared by optionally crosslinking;
2) When the addition of the cross-linking agent rc is necessary for the formation of the reversible gel, the stage in which at least one layer A is produced according to the following method;
In the range of 20 ° C. to 120 ° C., which corresponds to the liquid transfer - - at least one active chemical substance x, with optionally a solvent s _a, a binder y optionally and structural polymer c, gel Mixing at a temperature higher than the transition temperature (T-trans) to produce a solution,
- Structural polymer c, the active chemical substance x, at the same time a cross-linking agent rc with a mixture comprising a solvent s _a and binders y as required, mixed by spraying,
-Applying the solution on the layer obtained in stage 1), then cooling and rapidly crosslinking;
3) stage for applying the layers A and E in the order according to the desired order, layers A and E are separated by bonding layers Z optionally and in accordance with the layer A and the layer E is stage 1) and 2) is produced; and 4) the stage of making and applying the final elastomer barrier layer E carrying no or carries a binding agent y by evaporating the solvent s _e or water; after this stage, crosslinking optionally stage To implement. A method for producing a multilayer material comprising at least one layer A comprising an irreversible gel according to claim 1, characterized in that it comprises the following stages:
Applying a first elastomeric barrier layer E, which 1) does not carry or carries a binding agent y, the polymer e of claim 21 is dissolved in a solvent s _e as defined in claim 23, the solution on a suitable substrate _Prepared by evaporating the solvent se ; and optionally cross-linking;
2) At least one layer A is produced according to the following method;
- at least one active chemical substance x, with optionally a solvent s _a, solution prepared is mixed with a binder y structural polymer c and optionally,
-Mixing the crosslinking agent ic directly into the resulting solution;
-Applying the solution on the layer obtained in stage 1),
-Initiating crosslinking by photochemical and / or thermal routes or by contacting with a crosslinking accelerator;
3) stage for applying the layers A and E in the order according to the desired order, layers A and E are separated by bonding layers Z optionally and in accordance with the layer A and the layer E is stage 1) and 2) postcrosslinking this stage, if necessary; manufactured; a and 4) binders y the end of the elastomeric barrier layer E carrying no or carrier, the solvent s _e or the water stage of making and coating by vaporizing Perform the stage. A method for producing a multilayer material comprising at least one layer A comprising an irreversible gel according to claim 1, characterized in that it comprises the following stages:
Applying a first elastomeric barrier layer E, which 1) does not carry or carries a binding agent y, the polymer e of claim 21 is dissolved in a solvent s _e as defined in claim 23, the solution on a suitable substrate and evaporated the solvent s _e; stage that prepared by optionally crosslinking;
2) Stage for producing at least one layer A according to the following method;
- at least one active chemical substance x, with optionally a solvent s _a, solution prepared is mixed with a binder y structural polymer c and optionally,
- polymer c, introducing active chemicals x, simultaneously crosslinking agent ic a mixture comprising a solvent s _a and binders y if necessary,
-The solution is applied on the layer obtained in stage 1) and then rapidly crosslinked to induce film formation;
3) stage for applying the layers A and E in the order according to the desired order, layers A and E are separated by bonding layers Z optionally and in accordance with the layer A and the layer E is stage 1) and 2) is produced; and 4) the stage of making and applying the final elastomer barrier layer E carrying no or carries a binding agent y by evaporating the solvent s _e or water; after this stage, crosslinking optionally stage To implement. The tie layer Z comprises polymer z according to claim 22 with aromatic, aliphatic and alicyclic hydrocarbons, more polar compounds such as ether, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or ketone or alcohol and water or the process according to any one of claims 23 to 26, characterized in that it is manufactured by a solution in a solvent s _Z is selected from the group consisting of intermediate polar mixtures of evaporating the solvent s _Z or water . 28. A method according to claim 27, characterized in that the tie layer Z is photochemically initiated and subjected to thermal or chemical accelerated crosslinking. Layer A characterized in that it comprises a stage in which the structural polymer c is produced by in-situ polymerization by a thermal, photochemical or radiochemical route from a mixture of one or more monomers m and at least one active chemical substance x A method for producing a multilayer material comprising the irreversible gel according to claim 8. 30. A method according to claim 29, characterized in that the mixture further comprises at least one component, i.e. initiator i , one or more solvents sa, _a thickener f , a crosslinking agent ic or a binder y : 30. A process according to claim 29, wherein the monomer m is preferably selected from the group consisting of acrylics, acrylates, acrylamides, acrylic amines and their derivatives or vinyl pyrrolidone. 30. The process according to claim 29, wherein the number of monomers used is 1-10, preferably 1-4. In the case of thermally initiated polymerization, the initiator i is a peroxide family, such as benzoyl peroxide, an azonitrile family, such as azobisisobutyronitrile, or a redox pair, such as the method of claim 29 or 30, characterized in that selected from the group consisting of the pair _{S 2 O 8 / S 2 O} 5. 31. A process according to claim 29 or 30, characterized in that in the case of photochemically initiated polymerization, the initiator i is selected from the group consisting of the acetophenone family, benzoin derivatives or peroxide families. Thickener f is compatible with aluminum stearate, calcium linoleate paste, hydrogenated castor oil, triglycerides, bentonite type modified clay, polyol ester, silica, and a mixture of monomers 31. A polymer according to claim 29 or 30, characterized in that it is selected from the group consisting of a polymer having the same properties as the gelled polymer, for example a modified poly (acrylic acid), polymethacrylate or polyvinylpyrrolidone. the method of. 36. A stage comprising the production of layer A and layer E according to any of claims 23 to 35, wherein the chemical or physical treatment of layer A and / or layer E is carried out after application on a suitable substrate. The manufacturing method of the multilayer material of Claim 1 characterized by the above-mentioned. The chemical treatment is carried out by grafting or by chemical attack with an acid solution, and the physical treatment is carried out by impact of the film surface with ions, electrons or photons. Item 37. The method according to Item 36. Use as a coating for a substrate of multilayer material according to any of the preceding claims, in particular a substrate made of elastomer or plastic, or for the overformering of a rubbing seal. A glove that is coated with the multilayer material according to any one of claims 1 to 22. A finger cot, which is coated with the multilayer material according to claim 1. A condom coated with the multilayer material according to claim 1.

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